Cyclobutene phosphoric acid esters

ABSTRACT

NEW PHOSPHORIC ACID ESTERS WHICH CONTAIN AS ESTERIFYING RADICAL A CYCLOBUTENOL RADICAL WHICH IS FUSED TO A RING SYSTEM ARE PRODUCED FROM NOVEL INTERMEDIATES WHICH ARE A-HALOGENO-CYCLOBUTANONES FUSED TO A RING SYSTEM. THE NEW ESTERS ARE USEFUL AS PESTICIDES; A METHOD OF CONTROLLING PESTS WITH THE AID OF THE NEW COMPOUNDS AS WELL AS PESTICIDAL COMPOSITIONS CONTAINING THEM AS ACTIVE INGREDIENTS ARE ALSO DESCRIBED.

United States Patentfilhce 3,810,919 Patented May 14, 1974 3,810,919CYCLOBUTENE PHOSPHORIC ACID ESTERS Beat Biilmer and Kurt Riifenacht,Basel, Switzerland, assignors to Ciha-Geigy Corporation, Ardsley, N.Y.No Drawing. Original application Nov. 17, 1967, Ser. No. 683,784, nowPatent No. 3,600,474. Divided and this application Apr. 28, 1971, Ser.No. 50,007

Int. Cl. C07d 7/24 US. Cl. 260-345.2 3 Claims ABSTRACT OF THE DISCLOSURENew phosphoric acid esters which contain as esterifying radical acyclobutenol radical which is fused to a ring system are produced fromnovel intermediates which are u-halogeno-cyclobutanones fused to a ringsystem. The new esters are useful as pesticides; a method of controllingpests with the aid of the new compounds as well as pesticidalcompositions containing them as active ingredients are also described.

CROSS REFERENCE TO RELATED APPLICATION This is a division of applicationSer. No. 683,784, filed Nov. 17, 1967, now US. Pat. No. 3,600,474.

DESCRIPTION OF THE INVENTION The present invention concerns newphosphoric acid esters having a cyclobutene ring, processes for theproduction thereof and for the production of new a-halogencyclobutanones which serve as intermediates for making said novelesters, furthermore pesticidal compositions which contain the newphosphoric acid esters as active substances, as well as methods for thecontrol of pests using the new phosphoric acid esters or compositionswhich contain the same as active substances, and also processes for theproduction of the new pesticides.

Although cyclohexenyl and cyclopentenyl phosphoric and thiophosphoricacid esters have been produced in the past and their insecticidal actiontested (cf. e.g. Swiss Pat. No. 323,228, British Pat. No. 1,002,248, A.N. Pudovik, Zhur. Obschchei Khim. 25, pp. 2173-82 (1955) [C.A., 50,8487c (1956)], B. A. Arbuzow, Jzv. Akad. SSSR, 1961, pp. 2020-2028[C.A., 56, 11457f (1962)] and J. F. Lutsen-ko, Doklady Akad. Nauk. SSSR,135, pp. 860-863 (1960) [C.A., 55, l4287b (1961)], cyclobutenephosphoric acid esters have not been known hitherto. By this latter termas used in this application there are meant phosphoric acid esters whichare esterified by the radical of a cyclobutenol which is fused to a ringsystem. 7

It has now been found that such cyclobutene phosphoric acid esters ofthe General Formula I have excellent acaricidal, insecticidal andnematocidal properties. They are particularly valuable for theprotection of plants and stores and for soil disinfection. In addition,these new phosphoric acid esters are also suitable for the control ofpests, such as helminths or ticks, which are injurious to farm animals,domestic animals and pets.

In the General Formula 1:

R represents a lower alkyl radical, an unsubstituted phenyl radical or aphenyl radical substituted by one or several halogen atoms having anatomic number of at most 35 or by a lower alkyl radical,

R represents a lower alkyl radical,

R represents hydrogen, a halogen atom of an atomic number of at most 35,a lower alkyl radical, the phenyl radical or a phenyl radicalsubstituted by one or more halogen atoms up to the atomic number 35 orby a lower alkyl radical,

X and Y represent, independently of each other, the direct bond, oxygenor an group wherein R is a lower alkyl radical, and

A represents an unsubstituted or substituted, saturated orolefinically-unsaturated bridge having from 3 to 6 chain members, whichcontains as one chain member a carbon or an oxygen atom, the remainingchain members being preferably carbon atoms, and which bridge may be inits turn part of a carbocyclic ring system, in particular, in the lattercase, two adjacent carbon atoms of said bridge may pertain to aphenylene-(1,2) radical.

As lower alkyl radicals R, R R and R are meant those radicals havingfrom 1 to 5 carbon atoms, in particular a methyl, ethyl, propyl, butylor amyl radicals as substituent R or R a methyl, ethyl or propyl radicalas substituent R and a methyl or ethyl radical as substituent R.

The trimethylene, tetramethylene, pentamethylene and hexamethyleneradical are examples for saturated 3- to 6 membered aliphatic bridges A,whilst as olefinicallyunsaturated 3- to 6-membered aliphatic bridge A,for instance, the propenylene and butenylene radicals may be mentioned.As example for a 3- to 6-membered bridge A containing an oxygen atom aschain member there can be mentioned the trimethylenoxy radical and asexample of a bridges A may be substituted, for instance, by halogen theo-phenylene-methylene radical. The above listed bridges A may besubstituted, for instance, by halogen atoms of an atomic number of atmost 35, hydroxy or epoxy groups, an alkoxycarbonylthio oralkoxythiocarbonylthio group, or by a phenylthio radical anysubstituents of which are selected from halogen of an atomic number ofat most 35, lower albyl and nitro groups.

The new cyclobutene phosphoric acid esters of the General Formula I areproduced according to the present invention by reacting an a-halogencyclobutanone of the General Formula II wherein Hal represents a halogenatom up to the atomic number 35, and

R and A have the meanings given in Formula I,

wherein Z represents a lower alkyl radical, and R R X and Y have themeanings given in Formula I,

the reaction being performed in the presence or absence of a solvent ordiluent.

In the process accoridng to the invention, the following can be used,e.g. as intermediates of General Formula II:

7,7-dichlorobicyclo( 3 .2.0) -heptan-6-one, 7,7-dibromobicyclo (3 .2.0-heptan-6-one, 7,7-dichlorobicyclo 3 .2.0) -hept-2-en-6-one,7,7-dibromobicyclo (3 .2.0) -hept-2-en-6-one, I2,3-dibromo-7,7-dichlorobicyclo 3.2.0 -heptan-6-one,7,7-dichloro-2,3-epoxybicyclo( 3 .2.0) -heptan-6-one,8,8-dichlorobicyclo(4.2.0) -octan-7-one,

8, 8-dichlorobicyclo (4.2.0) -oct-2-en-7-one, 8,8-dichloro-2-oxybicyclo(4.2.0 -octan-7-one, 2,2-dichloro-7H-cyclobuta (a -indane,10,10-dichlorobicyclo(6.2.0)-decan-9-one,8,8-dichloro-2,S-methano-bicyclo (4.2.0) -oct-3 -en-7-one,7-chloro-7-phenyl-bicyclo (3 .2.0) -hept-2-en-6-one.

In addition, tat-halogen cyclobutanones which contain aromatic rings canbe used as starting materials. In these, however, the ring fused to thecyclobutane ring is preferably a non-aromatic homocycle or heterocycle.

The phosphoric acid esters of General Formula III which are preferred asstarting materials for the process according to the invention are thosein which each of R and R is a lower alkyl radical such as the methyl,ethyl, a propyl, butyl or amyl radical, R is a halogen atom of an atomicnumber of at most 35, the symbols X and Y are oxygen or also thosephosphoric acid esters in which Y is oxygen, X is the direct bond, R isan unsubstituted or, preferably, halogen-substituted phenyl radical, Ris a lower alkyl radical and R is a halogen atom of an atomic number ofat most 35.

In the processes according to the invention, the reaction occurs betweenphosphoric acid alkyl ester and a-halogen cyclobutanone while splittingoff halogenoalkane and simultaneous formation of a double bond (Perkowreaction). The reaction temperatures lie within the range of 60-160 C.The reaction of the tat-halogen ketones of Formula II with phosphoricacid esters of Formula HI is exothermic and, in some cases, thetemperature must be kept within the limits given by careful cooling. Thereaction can be performed in the presence of solvents or diluents whichare inert to the reaction components, e.g. saturated and aromatichydrocarbons such as cyclohexane, hexane, benzene, toluene, xylene etc.

In a modified process, cyclobutene phosphoric acid esters of GeneralFormula I wherein A is an olefinically unsaturated aliphatic bridgehaving 3 to 6 members are reacted with reactants capable of symmetricalor unsymmetrical addition to double bonds. Such reactants are, e. g.:catalytically activated hydrogen, halogen such as chlorine, bromine,iodine; ozone, hydrohalic acid, sulphuric acid,

sulphurous acid, sulphinic acids, nitrosyl chloride, sul

phenyl halide, hypohalite etc. These reactions can be performed in thepresence of solvents or diluents. In the phosphoric acid esters ofGeneral Formula I wherein A is an olefinically unsaturated aliphaticbridge having 3 to 6 members, also substitution reactions can beperformed, e.g. the Wohl-Ziegler halogenation (=Houben- Weyl, vol. 5,221 ff.) with N-halogen carboxylic acid amides or imides.

Intermediates of Formula II are obtained 'by a method known per se by1,2-cyclo-addition of halOgen ketenes to olefins [compare H. C. Stevenset al., J. Am. Chem. Soc,. 87, 5257 (1965) and L. Chosez. et al.,Tetrahedron Let- 4 ters, N9, [I 13 5 (1966) The halogen ketene can firstbe produced from thecorresponding a-halogen aeetyl chloride and atertiary organic nitrogen base or from the corresponding a-halogenacetyl bromide and zinc dust [according to W. T. Brady; J. Org. Chem.,31, 626 (1966)] in an inert solvent. After undesirable side productshave been removed from the solution of the halogen ketene the latter isreacted with an olefin Some of the a-halogen cyclobutanones of GeneralFormula H are known. Novel tat-halogen cyclobutanones correspond to theGeneral Formula IV D Hal Til:

wherein Hal represents a halogen atom up to the atomic number Rrepresents hydrogen, a halogen atom up to the atomic number 35, a loweralkyl radical, an unsubstituted phenyl radical or a phenyl radicalsubstituted by one or more halogen atoms of an atomic number of at most35 or by a lower alkyl radical,

A represents an unsubstituted or substituted, saturated orolefinically-unsaturated aliphatic bridge having 4 to 6 chain memberswhich may contain as one chain member an oxygen or carbon atom, theremaining chain members being preferably carbon atoms, and which bridgemay be in its turn part of a carbocyclic ring system, and are obtainedby reacting oleflns of the General Formula V wherein A' has the meaninggiven above, with a halogen ketone.

Rather than a halogen ketone, preferably a precursor thereof such as anu-haloge'n acyl halide is used in the presence of a tertiary nitrogenbase and a solvent or diluent. In certain cases it is of advantage toprepare the olefin together with the tertiary organic base and then addthe a-halogen acyl chloride. This method is chiefly suitable forolefins'which contain basic groups. The tertiary organic base, however,must be stronger than the olefin containing a basic group. Otherwise,the tertiary organic base is not used and instead double the amount ofolefin is used.

Either equimolar amounts of the reaction partners are combined or one ofthem, particularly the olefin can be usedin up to 10 times excess. If agreater excess of the olefin component is used it is often advantageousto leave out the solvent.

The cyclo addition is performed within a temperature range of 10 to C.,preferably from 20120 C.

If the a-halogen cyclobutanones of General Formula II have anolefinically-unsaturated radical as bridge A, then the addition andsubstitution reactions mentioned above such as catalytic hydrogenation,halogen and hydrohalic acid addition, the Wohl-Ziegler halogenation(loc. cit.) or the epoxidation, can be performed before the reactionwith esters of trivalent phosphorus. According to the invention, thereaction products so obtained can then be reacted in the mannerdescribed with trivalent phosphorus compounds.

,The phosphoricv acid esters of General Formula III can be obtained byknown processes (cf. Kosolapotf, Organophosphorus Compounds, Wiley,1950).

In the purified state, the new cyclobutene phosphoric acid esters ofGeneral Formula I are colorless oils which dissolve well in organicsolvents but are insoluble in water.

Tests of the action of compounds of the General Formula I on insects andspiders showed that these active substances are good to very goodcontact and stomach poisons and, at the same time, they have a markedsystemic action.

It has been found that the active compounds of General Formula I have anexcellent protracted action on insects of the families Muscidae,Stomoxidae and Culicidae, e.g. the polyvalent resistent and normallysensitive house flies (Musca domestica), stable flies (Stomoxyscalcitrans) and mosquitoes (e.g. Aedes aegypti, Culex fatz'gans,Anopheles stephensi), on insects of the families Curculionidae,Bruchidae, Dermestidae, Tenebrionidae and Chrysomelidae, e.g. granaryweevils (Sitophilus granaria), bean beetles (Bruchidius obtectus),larder beetles (Dermestes vulpinus), yellow meal worms (Tenebriomolitor), Colorado potato beetles (Leptinotarsa decemlineata) and theirstages of development, on the Pyralididae family, e.g. Mediterraneanflour moths (Ephestia kunniella), the Blattidae family, e.g. cockroaches(Phyllodromz'a germanica, Periplaneta amerioana, Blatte orientals), theAphididae family, e.g. bean aphids (Aphis fabae) and the Pseudococcidaefamily, e.g. citrus rnealybugs (Planococcus citri) and the familyLocustidae, migratory locusts (Locusta migratoria). Tests on the aphidsand locusts mentioned indicate an excellent systemic action.

In contrast thereto, 0,0 diethyl O cyelohexenyl phosphate [A. N.Pudovik, los. cit.] only has slight insecticidal properties.

In addition, the active substances according to the in vention have agood action on the larval andadult stages of spiders, e.g. of thefamilies of Tetranychidae, Ixodidae. Arachnidae, Argasidae.

Pests against which compounds falling under Formula I are found to beparticularly active are, for instance aphids, larvae of Aedes aegypti,cockroaches, ticks, e.g. a Diazinon-resistant strain of Boophilusmicroplus, Stomoxys maggots and soil nematodes, e.g. Melaidogynearenarza.

Effective amounts of these active substances ranged from 0.01 tomilligrams per square meter of an area in which the aforesaid pests hadto be controlled. Against nematodes and also in cases where systemicefiects had to be achieved, against Aphis fabae, amounts of up to 5 to20 g. per square meter, corresponding to concentrations of to 100 ppm.in a 20-cm. deep treated layer of soil are recommended.

In admixture with synergists and auxilaries having a similar action suchas succinic acid dibutyl ester, piperonyl butoxide, olive oil, peanutoil etc., the range of action of the active substances mentioned isbroadened and, in particular, the insecticidal and acaricidal action isimproved. In the same way, the insecticidal action can be substantiallybroadened and adapted to the prevailing circum stances by the additionof other insecticides such as phosphoric, phosphonic, thiophosphoric anddithiophosphoric acid esters and amides, carbamic acid esters,halogenated hydrocarbons, analogues of DDT active substances,pyrethrines and synergists thereof.

The following examples illustrate the production of the new cyclobutenephosphoric acid esters of the general Formula I. Where not otherwisestated, parts and percentages are given by weight, the temperatures arein degrees centigrade. The examples are not intended to limit the scopeof the invention EXAMPLE 1 A mixture of 50 parts of7,7-dichlorobicyclo(3.2.0)- hepten-(2)-one-(6) [L. Ghosez et al.,Tetrahedron Letters, No. 1, 135 (1966)] and 37 parts of trimethylphosphite is heated to 100 whereupon methyl cholride begins to splitoff. The heating bath is removed and the mixture is so cooled that thetemperature varies between 100 and 120. On completion of the exothermicreaction, the whole is stirred for 3 hours at 120. At the end of thistime, 7,7-

dichlorobicyclo(3.2.0) hepten-(2)-one-(6) is no longer visible by thinlayer chromatography.

After distillation in vacuo, 60 parts of 0,0-dimethyl-O- [7chloro-bicyclo(3.2.0)-hept-2,6-dienyl-(6)]-phosphate are obtained, B.P.9495/ 0.001 torr.

EXAMPLE 2 A solution of 32.6 parts of bromine in 240 parts of carbontetrachloride is added to a solution of 50 parts of 0,0 dimethyl-O-[7-chloro-bicyclo(3.2.0)-hept-2,-6-dienyl- (6)]-phosphate in 560 partsof carbon tetrachloride, the addition being made dropwise while coolingto 20. On completion of the addition, the reaction mixture is stirredfor another 2 hours at 20 after which the solvent and excess bromine aredistilled off. The residue is fractionated in vacuo.

The 0,0 dimethyl 0-[2,3-dibromo-7-chloro-bicyclo (3.2.0)hept-6-enyl-(6)l-Phosphate boils at 141-145" under 0.02 torr.

EXAMPLE 3 A solution of 22.6 parts of0,0-dimethyl-0-[7-chlorobicyclo(3.2.0)-hept-2,6-dienyl-(6) ]-phosphatein 400 parts of anhydrous dioxane is hydrogenated at room temperatureunder normal pressure in the presence of 4 parts of prehydrogenated Pt-C(5%) catalyst until no more hydrogen is taken up.

After filtering off the catalyst and distilling 01f the solvent, theresidue is fractionated in vacuo.

The 0,0 dimethyl-0-[7-chloro-bicycl0(3.2.0)-hept-6- en-(6)-yl]-phosphateboils at -92 under 0.005 torr.

EXAMPLE 4 A solution of 35.8 parts of 4-ch1orophenyl sulphenyl chloridein parts by volume of carbon tetrachloride is added dropwise at 05 to asolution of 50 parts of 0,0-dimethyl-0- [7 -chloro-bicyclo 3 .2.0)-hepta-2,6-dienyl- (6)]phosphate in 250 parts by volume of carbontetrachloride. The reaction mixture is then stirred for 2 hours at roomtemperature and then the solvent is distilled off in vacuo. The oilyresidue solidifies on cooling. After recrystallizing frombenzene/petroleum ether, the 0,0-dimethyl 0- [2 (3 ,7-dichloro-3 2')-4'-chlorophenyl-thiobicyclo(3.2.0)hepten (6)-yl-(6)]-phosphate melts at92- 93.

EXAMPLE 5 A solution of 200 parts of0,0-diethyl-0-[7-chloro-bicyclo-(3.2.0)-hept-2,6-dienyl- (6 ]-phosphatein 1000 parts of glacial acetic acid and 157 parts of 38.2% peraceticacid are left to stand for 4 days at room temperature. 2000 parts ofwater are then added to the mixture which is then extracted three timeswith 700 parts by volume of petroleum ether each time. After washingwith saturated bicarbonate solution and drying over potash, the solventis evaporated off in vacuo whereupon 21 parts of starting material areregained.

The aqueous phase is then extracted several times with ether. Afterwashing with bicarbonate solution and drying over potash, 138 parts of adark brown colored oil are obtained as crude product.

A sample of the crude 0,0-diethyl- O-[7-chloro-2,3-epoxy-bicyclo-(3.2.0)-hepten-(6)-y1-(6)l-Phosphate boils at 152-155/0.003 torr.

With the exception of the phosphoric acid esters Nos. 6 and 8 which areobtained by subsequently brominating the cycloalkadienyl phosphoric acidof Example 1 with bromine in carbon tetrachloride in the way describedin Example 2, the cyclobutene phosphoric acid esters of Formula Iwherein R R X, Y and A have the meanings listed in the following tableare prepared in the manner described in Example 1 on using equivalentamounts of the corresponding u-halogen cyclobutanone and thecorresponding trialkyl phosphite.

9 AD ESTERS NOS. 3 AND 4 AD ESTE'R NO. 6

A solution of 17 parts of bromine in 70 parts by volume of carbontetrachloride is added dropwise to a solution of 17.7 parts of7,7-dichloro-bicyclo(3.2.0)-hepten-(2)-one- (6) in 70 parts by volume ofcarbon tetrachloride. On completion of the addition, the reactionmixture is stirred for 2 hours at room temperature. The solvent is thendistilled off and the residue is fractionated.

1st fraction: 4-bromo-7,7-dichloro-bicyclo(3.2.0)-hepten- (2)-one-(6),B.P. 89-92/0.38 torr. 2nd fraction: 2,3-dibromo 7,7dichloro-bicyclo(3.2.0)-

hepten (2) one(6) (main fraction), B.P. 111-112l 0.3 8 torr.

AD ESTER 19 A solution of 13.6 parts of triethylamine in 60 parts ofcyclohexene is added dropwise While stirring to a solution of 120 partsof cyclohexene and 20 parts of dichloracetyl chloride. On completion ofthe addition, the reaction mixture is cooled and precipitatedtriethylamine hydrochloride is removed. The excess cyclohexene isdistilled off and the residue is fractionated in vacuo.

The 8,8-dichloro-bicyclo(4.2.0) octan 7 one boils at 46-47 under 0.001torr.

AD ESTERS NOS. 20 AND 21 A solution of 30.3 parts of triethylamine in150 parts of cyclo-octene is added dropwise, while stirring at 100, to asolution of 500 parts of cyclo-octene and 44.3 parts of dichloracetylchloride. On completion of the addition, the reaction mixture is cooledand the precipitated triethylamine hydrochloride is filtered oif. Thefiltrate is fractionated in vacuo. The 10,10 dichloro bicyclo(6.2.0)-decan-9-one boils at 100-102 under 0.005 torr.

AD ESTERS NOS. 22 AND 23 A solution of 55.5 parts of triethylamine in150 parts of light gasolene is added dropwise at 80 while stirring to asolution of 87 parts of indene and 80 parts of dichloracetyl chloride in440 parts of light gasolene. On completion of the addition, the reactionmixture is cooled and the precipitated triethylamine hydrochloride isfiltered off. The excess indene and light gasolene are distilled off invacuo. The residue which remains is crystalline.

Recrystallized from isopropanol, 2,2-dichloro-7H-(a)- indane melts at 75AD ESTERS NOS. 24 AND 25 A solution of 67 parts of triethylamine in 74parts of petroleum ether is added dropwise, while stirring at to asolution of 166 parts of dihydropyrane and 98 parts of dichloracetylchloride in 740 parts of petroleum ether. On completion of the addition,the reaction is stirred for some hours at room temperature and then theprecipitated triethylamine hydrochloride is filtered off. The filtrateis cooled with ice whereupon the desired reaction product crystallizesout. The 8,8-dichloro-2 oxa bicyclo(4.2.0)- octan-7-one melts at 70.

AD ESTER NO. 26

A solution of 60 parts of triethylamine in 320 parts of petroleum etheris added dropwise, while stirring at to a solution of 178 parts ofcyclopentadien and 103 parts of u-chloromandelic acid chloride in 960parts of petroleum ether. On completion of the addition, the reactionmixture is cooled and precipitated triethylamine hydrochloride isfiltered off. The filtrate is fractionated under vacuum. The7-chloro-7-phenyl-bicyclo(3.2.0)-hept-4-en- 6-one boils at -102under.0.07 torr.

AD ESTER NO. 27

31.8 parts of triethylamine in parts of diethyl ether are added whilestirring vigorously to a solution of 50 parts of cyclohexadien and 46.1.parts of dichloracetyl chloride in 150 parts of anhydrous diethyl ether,the addition being so made that the temperature of the reaction mixtureis 35. The triethylamine hydrochloride which precipitates after coolingis filtered oif, the non-reacetd cyclohexadien and the ether aredistilled OE and the oily residue is fractionated in vacuo.

The 8,8-dichloro-bicyclo(4.2.0)-octan 7 one boils at 69-70 under 0.6torr.

AD ESTER No. 28 i 100 parts of 7,7dichloro-bicyclo(3.2.0)-hepten-(2)-one-(6), 100 parts of N-bromosuccinimide, 0.5 part of dibenzoyl peroxideand 800 parts by volume of carbon tetrachloride are refluxed for 24hours. The precipitated succinimide is separated and the filtrate isdistilled in vacuo.

The 4 bromo-7,7-dichloro-bicyclo(3.2.0)-hepten-(2) one-( 6) distills atl071l0/ 3 torr and crystallizes. After recrystallization frombenzene/petroleum ether, it melts at 77-7 8.

The pesticides according to the invention are produced by known methodsby intimately mixing and milling active substances of General Formula Iwith suitable carriers, optionally with the addition of dispersingagents or solvents which are inert to the active substances. The newactive substances can be worked up into dusts, sprinkling agents,granulates (coated granulates, impregnated granulates and homogeneousgranulates), wettable powders, pastes, emulsions, solutions or aerosols.

The concentration of active substance in these compositions is OBI-80%by weight. The compositions according to the invention can be admixedwith other biocidal active substances or agents. Thus, to broaden theirrange of action, they can contain, in addition to the active substancesmentioned of the General Formula I, e.g. other insecticides, fungicides,bactericides, fungistatica, bacteriostatica or nematocides. In addition,the compositions according to the invention can also contain syntheticfertilizers, trace elements, etc.

The phosphoric acid esters of Formula I which have an anthelminticaction can be administered to the animals orally or via the abomasum inthe form of solid or liquid preparations, e.g. as solutions, emulsions,suspensions (drenches), powders, tablets, boluses and capsules. Theactive substances or compositions. containing them can also be added tothe feed or drinks.

The new active substances are used for soil disinfection in the form ofsolid or liquid agents. For soil disinfection those compositions areparticularly advantageous which provide an even distribution of theactive substance throughout a layer of 15 to 25 cm. deep soil. The modeof application and form of composition to be applied are dependent, inparticular, on the type of soil pests to be combated, the climate andsoil conditions. As the new active substances are not phytotoxic and donot have an adverse effect on the germination of seeds they can also beused without allowing for a so-called waiting time and they can be usedduring the growth of the cultivated plants.

The following forms of pesticides according to the invention illustratethe invention; where not otherwise expressly stated parts andpercentages are given by weight.

1 1 DUSTS The following components are used to produce (a) a and (b) a2% dust:

0,0-di-ethyl O [7-chl0ro-bicyclo(3.2.0)-hept-2,6-

dienyl- (6) ]-phosphate Highly dispersed silicic acid l Talcum 97 Theactive substances are mixed and milled with the carriers. The dustsobtained are suitable, e.g. for combating cockroaches and ants indoors.

SPRINKLING AGENT To produce a 25% sprinkling agent, the followingcomponents are used:

Parts 0,0-dimethyl O [7-bromo-bicyclo(3.2.0)-hept- 2,6-dieny1- 6)-phosphate Combination emulsifier (alkylaryl polyethyleneglycol/alkylaryl sulphonate calcium salt) 0.25 Kieselguhr 50 Calciumsulphate (aqueous) 24.75

The active substance is intimately mixed with the emulsifier and thekieselguhr and then the calcium sulphate is added. A sprinkling agent isobtained which is suitable in particular for soil disinfection.

WETTABLE POWDERS The following components are used to produce (a) a 50%and (b) a 10% wettable powder:

Parts 0,0-diethyl-O- [7chloro-2,3-dibromo bicyclo(3.2.0)-

hepten-(6)-yl-(6)]-phosphate 50 Naphthalene sulphonic acid/benzenesulphonic acid/ formaldehyde condensate Mixture of the sodium salts ofsaturated fatty alcohol sulphates Naphthalene sulphonicacid/formaldehyde condensate 5 Kaolin 82 The active substances areintimately mixed with the additives in suitable mixers and the mixtureis milled in suitable mills and rollers. Wettable powders are obtainedwhich can be diluted with water to form suspensions of any concentrationdesired. Such suspensions can be used to combat insects which injure byeating and sucking, as well as for combating ticks in pets and domesticanimals.

EMULSION CONCENTRATE To produce a 25 emulsion concentrate:

Parts 0,0 diethyl- O [7 chloro 4 bromo bicyclo- (3.2.0)hepta-2,6-dienyl-('6 ]-phosphate 25 Epichlorohydrin 2.5

Combination emulsifier (alkylaryl polyethylene glycol/alkylarylsulphonate sodium salt) Xylene 67.5

are mixed together. This concentrate can be diluted with Water to formemulsions in concentrations suitable for the protection of plants andstores. Such emulsions are suitable in particular for the combating ofticks in pets and domestic animals.

We claim:

1. A compound of the formula wherein R represents lower alkyl, phenyl,or chlorine-,bromine-,

or lower alkyl-substituted phenyl,

R represents lower alkyl,

R represents hydrogen, chlorine, bromine, lower alkyl,

phenyl, or chlorine-, bromine-, or lower alkyl-substituted phenyl,

each of X and Y represents independently of the other the direct bond,oxygen or the group in which R is lower alkyl.

2. A compound as defined in claim 1 which is 0,0- dimethyl O [8 chloro 2oxabicyclo(4.2.0)-oct-7- en-(7)yl]-phosphate.

3. A compound as defined in claim 1 which is 0, 0- diethyl 0 [8 chloro 2oxabicyclo(4.2.0)-oct-7- en(7)-yl]-phosphate.

References Cited UNITED STATES PATENTS 2,583,744 1/ 1952 'Schrader et al260343.2

JOHN M. FORD, Primary Examiner U.S. Cl. X.R.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3 810919 Dated May 14 1974 II II Inventor(S) Beat Bohner and Kurt RufenachtIt is certified that error appears in the above-identified patent andthat said Letters Patent are hereby corrected as shown below:

Insert the following information in the Heading:

Claims priority, application Switzerland, November 21, 1966,

Signed and sealed this 17th day of September 1974.

(SEAL) Attest:

MCCOY M. GIBSON JR. C. MARSHALL DANN Commissioner of Patents AttestingOfficer USCOMM-DC 60376-P69 f! U.5 GOVERNMENT PRINTING OFFICE: I5590-366-334.

FORM Po-wSo (10-69)

